Abstract:

A novel oxide material (MIN-I) comprising YO2; and X2O3,
wherein Y is a tetravalent element and X is a trivalent element, wherein
X/Y=O or Y/X=30 to 100 is provided. Surprisingly, MIN-I can be reversibly
deswollen. MIN-I can further be combined with a polymer to produce a
nanocomposite, depolymerized to produce predominantly fully exfoliated
layers (MIN-2), and pillared to produce a pillared oxide material
(MIN-3), analogous to MCM-36. The materials are useful in a wide range of
applications, such as catalysts, thin films, membranes, and coatings.

wherein d(Å)=interplanar spacing;I=peak height
intensity;I0=intensity of strongest peak;100 I/I0=relative peak
intensity;vs=greater than 60 up to about 100;s=greater than 40 up to
about 60;m=greater than 20 up to 40; andw=zero up to about 20.

9. The oxide material of claim 8 wherein the oxide material is
incorporated into a film or coating.

10. (canceled)

11. The oxide material of claim 9 wherein the film or coating is on a
support.

12. (canceled)

13. The oxide material of claim 8 comprising:YO2; andX2O3,
wherein Y is a tetravalent element and X is a trivalent element, wherein
X/Y=0 or Y/X=30 to 1000.

wherein the oxide material is a pillared oxide catalyst
andd(Å)=interplanar spacing;I=peak height intensity;I0=intensity
of strongest peak;100 I/I0=relative peak intensity;vs=greater than
60 up to about 100; andw=zero up to about 20.

25. The method of claim 17 further comprising combining the washed swollen
layered oxide material with a polymer to produce a composite.

26. (canceled)

27. The method of claim 25 wherein the composite is made with solvent
casting and the polymer is a polystyrene, polypropylene, polyolefin,
polymethacrylate, polyvinylalcohol, polyacrylamide, polycaprolactone, a
copolymer of ethylene, a copolymer of propylene, a copolymer of acetate,
poly(ethylene terephthalate), nylon, polysulfone, polyimide,
polyamidimide, polybenzaimidazole, or any combination thereof.

28. The method of claim 24 wherein the composite is made with melt
extrusion and the polymer is a polystyrene, polypropylene, polyolefin,
polymethacrylate, polyvinylalcohol, polyacrylamide, polycaprolactone, a
copolymer of ethylene, a copolymer of propylene, a copolymer of acetate,
poly(ethylene terephthalate), nylon or any combination thereof.

wherein d(Å)=interplanar spacing;I=peak height
intensity;I0=intensity of strongest peak;100 I/I0=relative peak
intensity;vs=greater than 60 up to about 100;s=greater than 40 up to
about 60;m=greater than 20 up to 40; andw=zero up to about 20.

30. The method of claim 29 wherein the polymer is removed by
depolymerizing the composite with calcination or by dissolving the
composite in a solvent to produce exfoliated layers and separating the
exfoliated layers.

31-32. (canceled)

33. The method of claim 29 further comprising forming a film or a coating
on a support.

34-40. (canceled)

41. A product made according to the method of claim 29.

42. A method of using the oxide material of claim 1 in a membrane.

Description:

[0001]This document claims the benefit of priority, under 35 U.S.C.
Section 119(e), of U.S. Provisional Patent Application Ser. No.
60/985,551, entitled NOVEL LAYERED ZEOLITE MATERIALS AND METHODS FOR
MAKING AND USING SAME, filed on Nov. 5, 2007 (Attorney Docket No.
600.708PRV), which is hereby incorporated by reference in its entirety.

BACKGROUND

[0003]Interest in porous lamellar solids, i.e., layered zeolite and
related materials, has dramatically increased recently due to the
discovery of new layered materials and new routes to modify existing
lamellar zeolites. Materials with nanoporous layers have structures which
are intermediate between crystalline nanoporous frameworks (e.g.,
zeolites) and typical layered materials (e.g., clay minerals). Each
nanoporous layer includes a porous network while the gallery between
layers allows for intercalation, pillaring and exfoliation.

SUMMARY

[0004]Embodiments of the invention provide novel oxide materials, thin
films and coatings. In one embodiment, each of the novel oxides, thin
films and coatings comprise YO2 and X2O3, wherein Y is a
tetravalent element and X is a trivalent element. In one embodiment
X/Y=0. In one embodiment, Y/X=30 to 1000. In one embodiment, Y/X=40 to
100. In one embodiment, Y/X=40 to 50. In one embodiment, Y is silicon.

[0005]The materials produced herein are characterized by various means,
such as x-ray diffraction (XRD) patterns. The peak height intensity, I,
and positions, as a function of 2theta (2θ), where θ is the
Bragg angle, are determined using computer algorithms known in the art
and associated with a diffraetometer. (Specifically, 2θ is
converted into d(obs.) using Bragg's law). From this information, the
relative peak intensities, 100 I/I0, where I0 is the intensity
of the strongest line or peak and interplanar spacing "d (obs.)" in
Angstrom Units (Å), may be determined.

[0006]In one embodiment, the novel oxide material is a novel swollen
material referred to herein as "MIN-1, which is derived from MCM-22(P)."
Surprisingly, and unlike conventional swollen MCM-22(P), MIN-1 is capable
of being unswollen into substantially its original form (e.g., with an
acid), such that it may be considered a reversibly swollen material. In
one embodiment, MIN-1 has a powder X-ray diffraction pattern (hereinafter
"XRD pattern"), comprising the values shown in Table 1A below:

wherein d(Å)=interplanar, spacing;I=peak height
intensity;I0=intensity of strongest peak100 I/I0=relative peak
intensityvs=greater than 60 up to about 100; andw=zero up to about 20.

[0008]Additional peaks may be revealed upon better resolution of the XRD
pattern, but none of said additional lines would have an intensity
greater than the line at the d(A) spacing of 12.3+/-0.14 or at
3.4+/-0.03, whichever is more intense. These values are different than
the x-ray diffraction pattern of swollen MCM-22(9) prepared by
conventional methods, as described herein.

[0009]MIN-1 can also be combined with a polymer to produce a nanocomposite
material designated previously as "MIN-2," containing predominantly
exfoliated layers together with a few intercalated crystals. (See U.S.
Patent Application Ser. No. 60/985,551, hereinafter "'551"). However, in
order to distinguish between a newer fully exfoliated and polymer-free
MIN-2 material described below, the original MIN-2 material discussed in
'551 is referred to herein as a "composite MIN-2" material or a
"polymer-MIN-2 nanocomposite.

[0010]In one embodiment, a "composite MIN-2" material is produced by
combining MIN-1 with a polymer having a glass transition temperature
below about 150° C., to produce a material having predominantly
exfoliated layers with a few intercalated crystals. In one embodiment,
the polymer is polystyrene. In one embodiment, the polymer is a
polypropylene, polyolefin, polymethacrylate, polyvinylalcohol,
polyacrylamide, polycaprolactone, a copolymer of ethylene, a copolymer of
propylene, a copolymer of acetate, a poly(ethylene terephthalate),
polysulfone, polyimide, polyamidimide, polybenzaimidazole, or any
combination thereof. The polymer may be further dissolvable in an organic
solvent, a polar nonprotic solvent or any combination thereof.

[0011]In one embodiment, the polymer is removed from composite MIN-2, such
as by depolymerization, to produce a novel, predominantly exfoliated
material free of polymer referred to herein as "exfoliated MIN-2" or
simply "MIN-2." MIN-2 is a powder containing highly crystalline,
nano-thick zeolite layers. In one embodiment, "MIN-2" has a XRD pattern
comprising the values shown in Table 2A below:

wherein d(Å)=interplanar spacing;I=peak height
intensity;I0=intensity of strongest peak100 I/I0=relative peak
intensityvs=greater than 60 up to about 100;s=greater than 40 up to about
60;m=greater than 20 up to 40; andw=zero up to about 20.

[0012]In one embodiment, MIN-2 has a XRD pattern comprising the values
shown in Table 2B below.

wherein d(Å)=interplanar, spacing;I=peak height
intensity;I0=intensity of strongest peak100 I/I0=relative peak
intensityvs=greater than 60 up to about 100;s=greater than 40 up to about
60;m=greater than 20 up to 40; andw=zero up to about 20.

[0013]Additional peaks may be revealed upon better resolution of the XRD
pattern, but none of said additional peaks would have an intensity
greater than the peak at the d(A) spacing of 12.1+/-0.13 or at
3.41+/-0.01, whichever is more intense.

[0014]In one embodiment, MIN-1 is pillared to produce a novel
catalytically active material analog to MCM-36, designated as MIN-3. In
one embodiment, MIN-3 has a XRD pattern comprising the values shown in
Table 3A below:

wherein d(Å)=interplanar spacing;I=peak height
intensity;I0=intensity of strongest peak100 I/I0=relative peak
intensityvs=greater than 60 up to about 100; andw=zero up to about 20.

[0016]Additional peaks may be revealed upon better resolution of the XRD
pattern, but none of said additional peaks would have an intensity
greater than the peak at the d(A) spacing of 12.2+/-0.14 or at
3.4+/-0.03, whichever is more intense.

[0017]In one embodiment, the oxide materials are incorporated into films
or coatings, which may be contained with a silica matrix. In one
embodiment, the films or coatings are supported, such as on an alumina
support.

[0018]In one embodiment, the invention further includes a method
comprising reversibly swelling an oxide material to produce an unwashed
swollen layered oxide material, the oxide material having a first layer
structure; and washing the unwashed swollen layered oxide material with
water to produce a washed swollen layered oxide material having a second
layer structure substantially the same as the first layer structure and a
X-ray diffraction pattern comprising:

wherein d(Å)=interplanar spacing;I=peak height
intensity;I0=intensity of strongest peak100 I/I0=relative peak
intensityvs=greater than 60 up to about 100; andw=zero up to about 20.

[0019]In one embodiment, the second layer structure is the same as the
first layer structure. In one embodiment, the oxide material is a layered
oxide material, such as MCM-22(P). The washed swollen layered oxide
material may be uniformly dispersed in a variety of organic solvents,
including, but not limited to, toluene, xylene and so forth, to form
stable dispersions useful in a variety of applications. In one
embodiment, the oxide material is swollen at room temperature.

[0020]In one embodiment, the washed swollen layered oxide material
comprises YO2 and X2O3, wherein Y is a tetravalent element
and X is a trivalent element, and X/Y=0. In one embodiment, Y/X=30 to
1000. In one embodiment, Y/X=40 to 100. In one embodiment, Y/X=40 to 50.
In one embodiment, Y is silicon.

[0021]In one embodiment, the invention further includes a method
comprising combining the washed layered swollen oxide material with a
polymer to produce composite MIN-2. A composite MIN-2 material has layers
of oxide material predominantly exfoliated by the polymer together with a
few intercalated crystals. Such a composite may be made through known
methods in the art, including, but not limited to, solvent casting or
melt extrusion, with the choice of method dependent on many factors, such
as the polymer used.

[0022]In one embodiment, the invention further includes a method for
removing the polymer from the composite MIN-2 material to produce MIN-2
powder having a XRD pattern, such as the pattern shown in Tables 2A and
2B.

[0023]Various methods for removing the polymer from composite MIN-2 may be
used. In one embodiment the composite MIN-2 is heated past its ceiling
temperature to cause the depolymerization. Polymer removal may also be
achieved by dissolution of the polymer in a solvent and separation of the
suspended layers from the dissolved polymer by filtration or
centrifugation. Polymer removal may also be achieved by simple
calcination in air. The resulting exfoliated oxide powder is expected to
be more stable and have improved properties as compared with conventional
exfoliated oxide materials.

[0024]In one embodiment, the invention further comprises pillaring MIN-1
to produce MIN-3 having an XRD pattern, such as the pattern shown in
Tables 3A and 3B. The resulting pillared oxide is expected to be more
stable than the known pillared zeolite material, MCM-36.

[0025]In one embodiment, the invention further comprises forming a film or
a coating on a support, such as an alumina or porous stainless steel
support, although the invention is not so limited. Any of the various
forms of the oxide material discussed herein may be used, including the
swollen, composite, polymer-free and pillared oxide materials. In one
embodiment, the film or coating comprises layers contained within a
silica matrix. In one embodiment, the invention further comprises a
product made according to any of the methods discussed herein.

[0026]In one embodiment, mixed matrix membranes are made by adding the
exfoliated MIN-2 powder into a polymer, such as with a solvent casting
step. Such membranes exhibit excellent separation properties. In one
embodiment, a thin film is made by depositing the exfoliated MIN-2 powder
onto a porous alumina support, such as with a layer-by-layer deposition
process. Such films are expected to provide excellent separation
properties.

[0027]In one embodiment, the invention further comprises using the various
novel oxide materials described herein as membranes for separation,
barrier, and corrosion protection applications.

[0028]These materials are also useful for improving the mechanical
strength of polymeric materials, as polymer nanocomposite membranes for
separations, as highly active catalytic materials, as coatings, and for
improving the flame resistance of various materials.

BRIEF DESCRIPTION OF THE DRAWINGS

[0029]FIG. 1 illustrates a novel scheme for reversibly swelling MCM-22(P)
to produce MIN-1, and for pillaring MIN-1 to produce MIN-3 in embodiments
of the present invention.

[0039]FIG. 5C shows a TEM image of MINI in an embodiment of the present
invention.

[0040]FIG. 5D shows a TEM image of MCM-22(PS-80).

[0041]FIG. 6A shows a HRTEM image of a MCM-22(P) material.

[0042]FIG. 6B shows a HRTEM image of MIN-1 in an embodiment of the present
invention.

[0043]FIG. 6C shows a HRTEM image of deswollen MCM-22(P) obtained by
acidification of MIN-1 in an embodiment of the present invention.

[0044]FIGS. 6D, GE and 6F show HRTEM images of MCM-22(PS-80) in
embodiments of the present invention.

[0045]FIG. 7A shows a XRD pattern of MIN-3 obtained by pillaring MIN-1,
including a second curve showing a five (5) times magnification in an
embodiment of the present invention.

[0046]FIG. 7B shows a XRD pattern of MCM-36 obtained by pillaring
MCM-22(PS-80), including a second curve showing a five (5) times
magnification in an embodiment of the present invention.

[0047]FIG. 8 is a TEM micrograph showing MIN-3 in embodiments of the
present invention.

[0048]FIG. 9 shows a N2 adsorption/desorption isotherm of (a) MCM-22
and (b) MIN-3 in embodiments of the present invention.

[0049]FIG. 10 shows a TEM image of the dispersion of MIN-1 in toluene in
embodiments of the present invention.

[0050]FIG. 11A shows a TEM micrograph of a composite MIN-2 material
prepared by solution casting in an embodiment of the present invention.

[0051]FIG. 11B shows a TEM micrograph of a composite MIN-2 prepared by
melt compounding under one set of conditions in an embodiment of the
present invention.

[0052]FIG. 11C shows a TEM micrograph of a composite MIN-2 prepared by
melt compounding under a second set of conditions in an embodiment of the
present invention.

[0053]FIG. 12 shows MUD patterns for an exfoliated MIN-2 material in an
embodiment of the present invention.

[0054]FIG. 13 shows a TEM micrograph of an exfoliated MIN-2 material in an
embodiment of the present invention.

[0055]FIG. 14A shows a cross-sectional view SEM image of a MCM-22/silica
film together with a schematic showing the flow of hydrogen and nitrogen
in an embodiment of the present invention.

[0056]FIG. 14B is a top view SEM image of the film in FIG. 14A in one
embodiment of the present invention.

[0057]FIG. 15A shows permeability of a MCM-22/silica film for various
gases in an embodiment of the present invention.

[0058]FIG. 15B shows the selectivity of a MCM-22/silica film for various
gas pairs in an embodiment of the present invention.

[0059]FIG. 16 is a schematic of transport paths for hydrogen and carbon
dioxide through a MCM-22 membrane made using MCM-22 disk-shaped crystals
in an embodiment of the present invention.

[0060]FIGS. 17A and 17B are SEM images of an exfoliated MIN-2 thin film
coating on alumina support prepared by a layer-by-layer (LBL) method in
an embodiment of the present invention.

[0061]FIG. 18 is a schematic of a membrane made using exfoliated MIN-2
layers in an embodiment of the present invention.

[0062]FIG. 19 is a schematic of a composite membrane comprising mesoporous
silica/MIN-2 in an embodiment of the present invention.

DETAILED DESCRIPTION

[0063]In the following detailed description of embodiments of the
invention, embodiments are described in sufficient detail to enable those
skilled in the art to practice them, and it is to be understood that
other embodiments may be utilized and that chemical and procedural
changes may be made without departing from the spirit and scope of the
present subject matter. The following detailed description is, therefore,
not to be taken in a limiting sense, and the scope of embodiments of the
present invention is defined only by the appended claims.

[0064]The Detailed Description that follows begins with a definition
section followed by a brief background, a description of the embodiments,
examples and a brief conclusion.

DEFINITIONS

[0065]As used herein, the term "MCM-22(P)" or "zeolite MCM-22(P)" (i.e., a
precursor of MCM-22 defined below) refers to a layered material comprised
of 2.5 nm thick sheets stacked in registry. Each sheet consists of a
bidimensional 10-member ring (MR) sinusoidal channel pore system and
large 12-MR cups on the crystal surface. These large cups are connected
to each other through double 6-MR.

[0066]As used herein, the term "MCM-22" refers to a material produced by
calcining MCM-22(P). Upon calcination, the layers of MCM-22(P) condense
together to form a 3-D framework structure. See also U.S. Pat. No.
4,954,325 to Rubin.

[0067]As used herein, the term "MCM-22(PS-80)" refers to the material
obtained by swelling MCM-22(P) according to methods described by Corma,
et al, Nature (London) 1998, 396, (6709), 353-356.

[0068]As used herein, the term "ITQ-2" refers to a conventional layered
material described in Corma, et al, Nature, 1998, 396, (6709), 353-356).
ITQ-2 comprises a material with exfoliated layer. However, layer
morphology and pore structure of this material is known to be partially
destroyed.

[0069]As used herein, the term "MCM-36" refers to a pillared layered oxide
material as described in U.S. Pat. No. 5,278,115 to Kresge (hereinafter
'115).

[0070]As used herein, the term "MIN-1" refers to a novel structure
prepared by swelling MCM-22(P) at room temperature and with successive
washings sufficient to obtain the XRD pattern shown in any of traces c to
e in FIG. 2.

[0071]As used herein, the term "exfoliated MIN-2" or "MIN-2," without
further qualification, refers to a predominantly exfoliated MIN-1.

[0072]As used herein, the term "composite MIN-2" or polymer MIN-2
composite" refers to MIN-1 combined with a polymer, i.e., MIN-1 in a
polymer matrix, resulting in at least 50% exfoliation of MIN-1.

[0073]As used herein, the term "MIN-3" refers to a MCM-36 analog obtained
by pillaring MIN-1.

[0074]As used herein, the term "swelling" without any further
qualification refers to increasing the thickness of the gallery by
introducing an ionic or non-ionic surfactant or one or more other guest
molecules into the gallery space.

[0075]As used herein, the term "intercalating" refers to a type of
swelling which involves the introduction of an ionic or non-ionic
surfactant or one or more other guest molecules into the gallery (space
between the layers) of a host structure without any major structural
changes in any layer of the host structure. The resulting product is an
intercalated phase. Structural changes which occur include increased
gallery spacing (i.e., thickness) and only minor changes of the layer
structure. Minor changes include, for example, a change in bond angles
and atomic positions with minimal or no corresponding change in atom
connectivity.

[0076]As used herein, the term "exfoliation" without any further
qualification refers to separating the layers of a layered material to an
extent such that layers lose correlation or registry with each other.

[0077]As used herein, the term "repeatedly washing" refers to a process of
dispersing a product in a suitable amount of freshly distilled water,
separating the product from water by centrifugation, removing the water
from the centrifuge, and then repeating the entire process again until
the desired result is achieved. Such a desired result includes, for
example, washing the swollen material having a XRD pattern shown in trace
b of FIG. 2 until it converts into MIN-1 with a XRD pattern shown in any
of traces c to e FIG. 2.

[0078]As used herein, the term "ceiling temperature" refers to a
temperature above which a polymer is thermodynamically unstable and
disintegrates into monomer molecules.

[0079]As used herein, the term "depolymerization" refers to a process of
converting a polymer to its monomer or other small and volatile
molecules. Depolymerization is typically achieved by heating a polymer
above its ceiling temperature.

[0080]As used herein, the term "film" refers to a thin film having a
thickness of less than about 10 micron.

[0081]As used herein, the term "membrane" refers to a film capable of
performing separations.

[0082]As used herein, the term "zeolite" refers to a crystalline
microporous oxide material.

BACKGROUND DISCUSSION

[0083]MCM-22(P), the precursor to MCM-22, consists of stacks of layers
which can be swollen, and subsequently pillared with silica (i.e. MCM-36)
or exfoliated to produce catalytically active materials (ITQ-2).

[0084]Fabrication of polymer nanocomposites with layered materials
requires intercalation of polymer chains in between the layers. To
facilitate the intercalation, layered materials (e.g., clays) are often
swollen with organic surfactant to increase the inter-layer spacing. The
increased inter-layer spacing allows intercalation of polymer chains
resulting in nanocomposites with intercalated and/or exfoliated
morphology.

[0085]Conventional swelling procedures, however, result in significant
degradation of crystal morphology (i.e., greater than about 50 wt %),
along with partial loss of crystallinity (i.e., greater than about 50 wt
%), and dissolution of the crystalline phase (larger than about five (5)
wt %). Therefore, materials derived from swollen MCM-22(P). MCM-36 and
ITQ-2, are known to have reduced crystallinity.

[0086]For example, swelling of MCM-22(P) by treatment with tetrapropyl
ammonium hydroxide (TPAOH) and cetyltrimethylammonium bromide (CTAB) at
elevated temperature and high pH results in layer fragmentation in excess
of about 50% along with partial dissolution of the framework silica,
i.e., in excess of about five (5) wt %. There is also a significant
reduction in Si/Al ratio (from 47 to 13) as a result of silica
dissolution. Moreover, the amorphous silica produced by the dissolution
of crystals may have an undesirable influence over the transport and
separation properties of the membrane and may also cause processing
problems during nanocomposite fabrication (e.g., due to aggregation).

DESCRIPTION OF EMBODIMENTS

[0087]Embodiments of the invention provide novel oxide materials referred
to herein as MIN-1, composite MIN-2, MIN-2 and MIN-3 and methods of
making and using same. These materials are useful in a number of
applications, including as films, which are useful in separation,
barrier, and corrosion protection applications. These materials are also
useful for improving the mechanical strength of polymeric materials, as
polymer nanocomposite membranes for separations, as highly active
catalytic materials, as coatings, and to improve flame resistance of
various materials. The novel materials described herein have improved
properties in all of the aforementioned applications as compared to
conventional zeolites.

[0088]The present invention further includes various methods for producing
the novel materials described herein. In one embodiment, the invention
comprises a method for producing nano-thick layers of a zeolite material
by separating layers (i.e., exfoliating the layers) present in a swollen
zeolite material in a polymer matrix, such as by a melt compounding
technique, and then removing the polymer by depolymerization. The
resulting material comprises high surface area fully exfoliated
nano-thick layers, i.e., an exfoliated zeolite. In one embodiment, the
resulting material is MIN-2, as defined herein.

[0089]In contrast to conventional exfoliated materials, destruction of the
pore structure of the zeolite layers in these novel materials is
significantly reduced. In one embodiment, the pore structure is retained
completely intact. In one embodiment, the pore structure is retained
substantially intact, i.e., such that over 90% of the original pore
structure is retained. Such improved pore structure is expected to
produce higher selectivity in products obtained from certain catalytic
reactions, including, but not limited to, xylene isomerization, vacuum
gasoil cracking and alkylation of benzene.

[0090]The novel materials further exhibit higher preservation of crystal
morphology. In one embodiment, crystal morphology is retained completely
intact. In one embodiment, crystal morphology is substantially intact,
i.e., such that over 90% of the original crystal morphology is retained.
Retaining such crystal morphology reduces layer fragmentation, thereby
producing high aspect ratio layered materials, i.e., an aspect ratio of
at least about ten (10) or higher, such as up to at least about 25. High
aspect ratio nano-thick layers are highly desirable for polymer based
nanocomposites and thin zeolite films. A high aspect ratio imparts
greater separation capabilities to a nanocomposite even at small zeolite
loadings, i.e., zeolite loadings as low as about two (2) wt %. A high
aspect ratio further allows formation of continuous coatings with more
uniform coverage of substrates as compared to low aspect ratio materials.

[0091]The novel materials further have a high silica content of at least
about 80 wt % of starting material. In one embodiment, the silica content
is greater than about 90 wt % up to about 99 wt % of starting material.
This is in contrast to conventional methods, in which as much as about 70
wt % of the silica is dissolved, thus significantly reducing the silica
content. As a result, the novel materials discussed herein are expected
to be more stable and more selective than conventional zeolite catalysts
for a variety of catalytic applications.

[0092]MIN-1

[0093]In one embodiment, MCM-22(P) is swelled under mild conditions
without disruption of the layered structure and repeatedly washed with
water, such as distilled water, to produce a novel swollen material
designated as MIN-1. This material has a novel XRD pattern as shown above
in Tables 1A and 1B. Such a diffraction pattern is in contrast with the
diffraction pattern for swollen MCM-22(P) as shown in Table 5 of '115.
(See, for example, col. 8, lines 1-19 of '115). Applicant is the first to
report additional peaks in a swollen layered oxide material derived from
MCM-22(P) with a d(Å) spacing greater than a line at 12.41±0.25
Å and less than a line at 32.2 Å, and an intensity comparable to
that of the 12.41±0.25 Å line. For example, see the peaks listed
in the second and third entries of Tables 1A and 1B. Specifically, for
Table 1A: d(Å.)=20±0.38; 100 I/I0=w and
d(Å)=13.4±0.17; 100 I/I0=w. For Table 1B: d(Å)=20.0;
100I/I0=w and d(Å)=13.4; 100 I/I0=w. See FIG. 2 in Example
1 which shows XRD curves for MIN-1 and other materials. Applicant is also
the first to report additional peaks in a swollen layered oxide material
derived from MCM-22(P) with a d(Å) spacing greater than a line at
12.3±0.14 Å and less than a line at 40.7±1.8 Å and an
intensity comparable to that of the 12.3±0.14 Å line.

[0094]In one embodiment, a method comprising swelling MCM-22(P) without
altering the crystal morphology and layer structure and preserving the
high aspect ratio of the layers with minimal dissolution of framework
silica is provided. In one embodiment, the method comprises using
cetyltrimethylammonium bromide (CTAB) and tetrapropylammonium hydroxide
(TPAOH) at room temperature with multiple washings to produce swollen
MCM-22(P), designated herein as "MIN-1." The resultant novel material
designated MIN-1 is highly ordered with increased interlayer spacing and
a distinct XRD pattern as shown in Tables 1A and 1B. In one embodiment,
the swelling process does not disrupt the framework connectivity present
in the parent MCM-22(P) material.

[0095]As noted above, with the reduction in fragmentation of layers by the
swelling procedure described above, high aspect ratio layered materials
result. Such materials are highly desirable for polymer based
nanocomposites and thin films, e.g., thin zeolite films. Additionally, a
high aspect ratio imparts greater separation capabilities to
nanocomposites, even at small oxide loadings. A high aspect ratio also
allows formation of continuous coatings with more uniform coverage of
substrates.

[0096]Surprisingly, and in contrast to known methods of swelling, the
novel method of swelling described herein is reversible. Specifically,
the swollen MIN-1 material may be converted back (deswollen) to
MCM-22(P). The demonstrated reversibility of the novel MIN-1 material
described herein verifies that the layer structures in MCM-22(P) are
preserved in the MIN-1 material. In contrast, MCM-22(P)-derived
MCM-22(PS-80) cannot be converted back to MCM-22(P).

[0097]In one embodiment, MIN-1 is uniformly dispersed in a variety of
organic solvents to form stable dispersions. Such solvents include, but
are not limited to, toluene, xylene and so forth, to form stable
dispersions. In one embodiment, stable dispersions of these materials are
used for a variety of applications, including, but not limited to, MIN-1
zeolite films produced by simple casting techniques for separation
applications and as corrosion resistant coatings. In one embodiment,
MIN-1 is dispersed in water or other polar solvents and solvent mixtures
to form multilayer films using any known method, such as layer-by-layer
ionic assembly.

[0098]Composite MIN-2

[0099]In one embodiment, MIN-1 may also be exfoliated within a polymer
matrix to produce a nanocomposite designated herein as "composite MIN-2"
or "polymer MIN-2 nanocomposite," as defined above. Any suitable polymer
can be used to produce the nanocomposite. The polymer may be further
dissolvable in an organic solvent, a polar nonprotic solvent or any
combination thereof.

[0100]In one embodiment, a novel composite MIN-2 material is made using a
polymer having a glass transition temperature below 150° C. In one
embodiment, a novel composite MIN-2 material is made by melt extrusion
using a polypropylene, polyolefin, polystyrene, polymethacrylate,
polyvinylalcohol, polyacrylamide, polycaprolactone, a copolymer of
ethylene, propylene or acetate, a poly (ethylene terephthalate), nylon,
or any combination thereof. In one embodiment, the novel nanocomposite
material is made with solution casting using any polymer noted above or
polysulfone, polyimide, polyamidimide, polybenzaimidazole and other
polymers which are dissolvable in organic or polar nonprotic solvents.
These materials exhibit an exfoliated morphology of layers.

[0101]Such materials are useful for a wide variety of applications as
discussed herein, including, but not limited to, membrane based
separation applications and for improving mechanical properties of
polymers.

[0102]Exfoliated MIN-2

[0103]In one embodiment, a novel exfoliated material designated herein as
"MIN-2" is produced from composite MIN-2 by heating composite MIN-2 to
above its ceiling temperature. In one embodiment, any remaining
fragments, including any remaining monomer are removed, such as with
vacuum and/or calcination treatments. MIN-2 also has a novel XRD pattern
as shown above in Tables 2A and 2B.

[0104]In one embodiment, the novel swelling procedure described herein
does not reduce the silica content of the zeolites or otherwise minimizes
silica reduction, and otherwise affects the crystal structure to a lesser
extent than the conventional process, the resulting MIN-2 powder is
likely to exhibit improved catalytic and stability properties as compared
to ITQ-2.

[0105]In one embodiment, the exfoliated MIN-2 is added to a polymer via a
solvent casting step to produce mixed matrix membranes having separation
capabilities (See Example 4). In one embodiment, the novel-MIN-2 material
is deposited layer-by layer to form an inorganic membrane in a process
referred to as layer-by-layer assembly (LBL). (See Example 6).

[0106]LBL is a method of thin film deposition which is useful for
oppositely charged polymers and for making polymer-nanoparticle films.
LBL can be applied to a variety of water soluble materials and is
especially suited for the fabrication of stratified thin films in which
layers of nanometer thickness are organized in a specific order. Such
materials in one layer have an affinity for materials in adjacent layers
via electrostatic interaction, van der Waal's forces or hydrogen bond
forces.

[0107]Typically, layer-by-layer films are assembled on a solid substrate
material. Deposition of the film material onto the substrate is performed
in a cyclic manner, made possible by the overcompensation of surface
charge which often takes place when polyelectrolytes and other high
molecular weight species are adsorbed on a solid-liquid interface. For
example, a polyelectrolyte-nanoparticle film may be deposited on a
substrate by repeating the process of: 1) immersion of the substrate in
an aqueous solution of polyelectrolyte; 2) washing with neat solvent and
drying; 3) immersion in an aqueous dispersion of nanoparticles; and 4)
final washing with neat solvent and drying. This process is repeated as
necessary, until the required numbers of layers are deposited to obtain
the specific properties of the desired material.

[0108]In one embodiment, the exfoliated MIN-2 is deposited onto a porous
alumina support to produce a thin film. Such films are expected to have
superior separation performance, as discussed in Prophetic Example 7. A
demonstration of the performance of MCM-22/silica films in Example 5
further confirms the expected superior separation performance expected
with the MIN-2 materials.

[0109]MIN-3

[0110]In one embodiment; MIN-1 is pillared to produce a novel
catalytically active material analog to the MCM-36 material shown in
'115, designated herein as MIN-3. This material also has a novel XRD
pattern as shown above in Tables 3A and 3B. This diffraction pattern is
in contrast with the diffraction pattern for pillared MCM-22(P) as shown
in Table 7 of '115 (See, for example, col. 8, lines 40-66). Applicant is
the first to report additional peaks in a pillared layered oxide material
with a d(Å) spacing greater than a line at 12.38±0.25 Å, less
than a line at 32.2 Å, and an intensity comparable to that of the
12.2±0.14 Å line. For example, see the peaks listed in the second
and third entries of Tables 3A and 3B. Specifically, for Table 2A:
d(Å)=20.6±0.4; I/I0=w and d(Å)=15.1±0.21; I/I0=w.
For Table 3B: d(Å)=20.57; I/I0=w and d(Å)=15.09;
I/I0=w. Applicant is also the first to report additional peaks in a
pillared layered oxide material derived from MCM-22(P) with a d(Å)
spacing greater than a line at 12.2±0.14 Å and less than a line at
43.9±1.9 Å and an intensity comparable to that of the 12.2±0.14
Å line.

[0111]As noted above, since the novel swelling procedure described herein
minimizes or eliminates reduction of silica content, and otherwise
affects the crystal structure to a lesser extent than the conventional
process, the resulting pillared material, MIN-3, is likely to exhibit
improved catalytic and stability properties than the conventional
pillared catalytic material MCM-36.

[0112]The invention will be further described by reference to the
following examples, which are offered to further illustrate various
embodiments of the present invention. It should be understood, however,
that many variations and modifications may be made while remaining within
the scope of the present invention.

Example 1

[0113]In this example MCM-22(P) is synthesized and then swollen at room
temperature to form a highly ordered material designated herein as MIN-1.
As demonstrated herein, there is no destruction of crystal morphology in
MIN-1 that can be detected by microscopy investigation, although
elemental analysis shows a small decrease (i.e., <ten (10) %) of
silicon from framework, i.e., original crystalline morphology is
retained. The reversibility of the swelling step is also demonstrated in
Example 1. MIN-1 was also successfully pillared to produce an analog of
MCM-36 designated herein as MIN-3. These steps are depicted in the scheme
shown in FIG. 1.

[0115]Stable dispersions of MIN-1 were also prepared in toluene, xylene,
benzene and acetone. An intercalated/exfoliated nanocomposite starting
with polystyrene and MIN-1, referred to herein as a composite MIN-2, was
also produced.

Synthesis of MCM-22(P)

[0116]MCM-22(P) was synthesized using the method described by Corma et
al., Journal of Catalysis 1999, 186, (1), 57-63 and Corma, et al, Nature
(London) 1998, 396, (6709), 353-356, (hereinafter "Corma 1998 and 1999").
0.72 g of sodium aluminate (MP Biomedicals, USA) and 2.48 g of sodium
hydroxide (97+%, Fisher-Scientific, Watham, Mass.) were dissolved in 311
g of distilled water. Subsequently, 19.1 g of hexamethyleneimine (HMI)
(Sigma-Aldrich, St. Louis, Mo.) and 23.6 g of fumed silica (Cab-o-sil M5,
Cabot Corp., Boston, Mass.) were added to the mixture. The mixture was
allowed to stir for 5 h at room temperature using a magnetic stirrer,
followed by 11 days in rotating Teflon®-lined steel autoclaves at
408° K. The crystalline product obtained after 11 days was
collected by centrifugation at 10,000 rpm followed by "repeatedly
washing" with distilled water as defined herein until the pH of washing
water became less than 9. A portion of the crystalline product was
calcined at 540° C. under air for 12 h to produce MCM-22.

[0117]MCM-22(P) was swollen with CTAB (Sigma-Aldrich, St. Louis, Mo.) at
room temperature under high pH conditions. The composition of the
swelling mixture was the same as reported by Corma 1998 and 1999, among
others. Nine (9) g of aqueous slurry of MCM-22(P) (20 weight percent
solids) was mixed with 35 g of an aqueous solution of 29 weight percent
CTAB and 11 g of an aqueous solution of 40 weight percent TPAOH (Alfa
Aesar, Wardhill, Mass.). The pH of the resulting mixture was 13.8. The
mixture was stirred using a magnetic stirrer for 16 h at room
temperature, after which the particles were recovered by repeated cycles
of centrifugation (IEC Multi, Thermo Fisher Scientific, Waltham, Mass.)
and water washing (10 min centrifugation at 10,000 rpm, removing water
and redispersion in fresh distilled water). The number of
(centrifugation/Water washing) cycles was systematically varied from 10
to 40 to study its effect on the recorded XRD patterns. For comparison, a
portion of MCM-22(P) was also swollen at elevated temperature (80°
C.) following the procedure reported by Corma 1998 and 1999.

[0118]Pillaring of the swollen material was performed according to the
procedure reported by Barth, J.-O.; Kornatowski, J.; Lercher, J. A.
Journal of Materials Chemistry 2002, 12, (2), 369-373. One (1) g of
swollen MCM-22(P) powder was mixed with 5 g of TEOS (tetraethoxysilane,
Sigma-Aldrich), stirred for 25 h at 351 K under an argon atmosphere, then
filtered and dried at room temperature. The dried solid (0.5 g) was
hydrolyzed with water (5 g, pH˜8, controlled with sodium hydroxide
(97+%, Fisher-Scientific, Waltham, Mass.) for 6 h at 313 K, and then
filtered, dried at 300° K. and calcined at 723° K. under
N2 flow (140 ml min-1) for 6 h and finally at 823° K.
under air for 12 h (temperature ramp rate of 2 K/min).

"MIN-2 Composite" Fabrication

[0119]Nanocomposite from Solution Casting Techniques

[0120]Nanocomposites of room temperature swollen MCM-22(P) and polystyrene
were prepared using solvent casting technique known in the art (see Choi
S. et. al, Journal of Membrane Science, 2008, (1-2), 145-152). A two (2)
weight percent dispersion of swollen MCM-22(P) was prepared in toluene
(Sigma-Aldrich). To assist homogeneous dispersion, the mixture was
subjected to ten (10) cycles of sonication (Branson 5510, Emerson
Electric Co., St. Louis, Mo.), and refluxing (6 h sonication, 6 h
refluxing). The resulting dispersion (1 g) was mixed with 1 g of 2 weight
percent polystyrene (Mn=5400) solution in toluene and stirred using
a magnetic stirrer for 5 days. Subsequently, the mixture was heated for 2
h at 110° C., followed by addition of 5 g of 20 weight percent
solution of polystyrene (Mw=45000, Sigma-Aldrich), further heating
(2 h, 110° C.), sonication (1 h) and finally spreading the
solution on a Teflon® surface (15 cm×10 cm). The solvent was
evaporated slowly over a period of 5 days and the composite was peeled
off the surface.

Nanocomposite from Melt Compounding Techniques

[0121]Nanocomposites were prepared by melt blending in a DACA Mini
Compounder vertical, co-rotating twin screw extruder (DACA Instruments,
Santa Barbara, Calif.), with a re-circulation channel. Polystyrene (3.8
g, Mw=45000, Sigma-Aldrich) and MIN-1 (0.16 g) were mixed manually
and loaded into the compounder preheated to 120° C. The mixture
was blended at a screw speed of 350 rpm for 15 min under nitrogen and
subsequently extruded out. A circular disc (25 mm×1 mm) was
prepared by compressing the extrudate 1000 psi and 150° C. for 10
min.

Characterization Methods

[0122]The silicon and aluminum contents of MCM-22(P), and of the novel
swollen materials (MIN-1), were determined by Galbraith Laboratories,
Knoxyille, Tenn.

[0124]Thermogravimetric analysis (TGA) was performed to estimate the
amount of organic contents in MCM-22(P) and novel swollen materials
(MIN-1). Experiments were carried out under air in the temperature range
of 110-800° C. (heating rate 10° C./min on a Perkin-Elmer
TGA-7 analyzer (Perkin Elmer, Waltham, Mass.).

[0126]A FEI Tecnai G2 F30 transmission electron microscope (TEM) (FEI Co.,
Hillsboro, Oreg.) equipped with a charge couple device (CCD) and operated
at. 300 kV was used for direct imaging of various samples. Samples were
prepared by simply sprinkling the powders onto a carbon coated copper
grid. For imaging swollen MCM-22(P) from toluene dispersions, a few
droplets were placed on a copper grid and allowed to air dry. For one of
the polymer nanocomposites, a JEOL 1210 microscope (JEOL, Tokyo, Japan)
operating at 120 kV was used for visualization. A Reichert Ultracut S
Ultramicrotome (Leica Microsystems GmbH, Wetztar, Germany) equipped with
a diamond knife was used for TEM sample preparation to obtain 50-80 nm
thick slices of nanocomposite.

[0128]XRD patterns of MCM-22(P) before and after swelling and repeated
centrifuging/washing are reported in FIGS. 2A and 2B. The XRD pattern for
MCM-22(P) (FIG. 2A, trace a) is in agreement with those reported in the
literature. The swollen product shows a shift of the 001 peak to lower
angles (FIG. 2A traces b-e) indicating an increase in layer spacing from
27 Å to about 42 Å. Peaks 220 and 310 are unaffected by swelling,
indicating preservation of the crystal structure within the layer. The
hid peaks along the c-axis (perpendicular to layers) either disappeared
or became broader due to the changes in the crystal structure. The 101
and 102 reflections merge together to form a broader peak, as reported in
the literature (See, e.g., Roth, W. J.; Vartuli, J. C. Studies in Surface
Science and Catalysis 2002, 141, (Nanoporous Materials III), 273-279).

[0129]Traces b-e in FIG. 2A show the evolution of the swollen structure
produced by "repeatedly washing" as defined herein. The swollen material
after 10 cycles of washing (Trace b) shows a new peak around a 2θ
value of 5.5°. Further washings resulted in disappearance of this
peak and emergence of two new peaks around 2θ angles of 4.5°
and 6.5°. Also, the 001 peak shifts towards slightly higher angles
(FIG. 1B). The two new peaks can be indexed as 002 and 003 based on the
position of the 001 peak. These peaks are not present in MCM-22(P)
swollen at elevated temperature (MCM-22(PS-80)) according to methods of
Corma 1998 and Corma 1999 (FIG. 1A, trace g). Also, the peaks are much
broader in MCM-22(PS-80), indicating a greater degree of disorder. The
room temperature swelling and repeated washing procedure (as described
herein) results in a novel expanded material (MIN-1) with a XRD pattern
as shown in FIGS. 2A and 213, traces c-e) having less broadening of peaks
as compared to MCM-22(PS-80). In addition, reflections 002 and 003 were
obtained, indicating long range order of layers in the swollen material.

[0130]FIG. 3 shows TGA curves for (1) MCM-22(P); swollen material after
(2) 10 washes, (3) 20 washes and (4) 40 washes; (5) deswollen material
obtained by acidification of MIN-1. The TGA curves (FIG. 3, (2)-(4))
reveal that repeated washings result in a decrease in the organic
content, presumably due to removal of CTAB. It is thought that partial
removal of CTAB, which might be loosely held in between the layers,
results in a more ordered lamellar swollen structure MIN-1 (as evidenced
by the emergence of 002 and 003 peaks noted in FIG. 2A).

Si/Al Ratio

[0131]The pH at the end of the room temperature swelling procedure was
found to be approximately equal to the starting pH of 13.8. On the other
hand, the swelling procedures at 80° C. resulted in a
significantly lower of 13. These observations can be explained by
comparing the Si/Al ratio of the respective materials. MCM-22(P) had a
Si/Al ratio of 46.7 as compared to 43.2 for MIN-1 and 11.8 for
MCM-22(PS-80). The decrease in Si/Al ratio as a result of swelling
indicates some dissolution of framework silica. The dissolved silica
forms mono silicic acid and other oligomeric silicates in the solution,
which on deprotonation, decrease the pH of the solution. Greater
dissolution occurs at elevated temperature.

Reversible Swelling

[0132]An unexpected and remarkably surprising feature of the room
temperature swelling procedure is that the process can be reversed by
acidification, i.e., reversible swelling is unexpectedly possible. FIG.
2A (trace f) shows the XRD pattern of the material obtained by
acidification of MIN-1, which appears to be same as that of MCM-22(P).
The TGA curve for this material (FIG. 3, trace (5)) shows considerably
lower organic content than MIN-1, which suggests the removal of CTAB as a
result of acidification. The MUD pattern and the TGA analysis suggest
that the acidification results in exchange of CTAB for protons and the
layers reassemble to form the MCM-22(P) structure with a characteristic
layer spacing of 2.7 nm.

[0133]Reversibility of the swelling suggests that HMI, initially present
in MCM-22(P), remains in between the layers after swelling and directs
the reassembly of the layers to the original MCM-22(P) structure upon
CTAB removal. Such reversibility does not occur with MCM-22(PS-80),
possibly because the layers are broken due to partial dissolution of
framework silica.

Electron Microscopy

[0134]SEM images Obtained from the precursor and swollen materials are
shown in FIGS. 4A, 4B, 4C and 4D. The MCM-22(P) crystals in FIG. 4A are
thin rounded flakes, less than a micron in diameter. Swelling at room
temperature, together with 10 and 40 subsequent washes, does not result
in any significant changes in the crystal morphology as evidenced by
comparing FIGS. 4A, 4B and 4C. However, there are differences in the XRD
patterns (FIGS. 1A and B, trace b and trace e) noted above. Swelling at
an elevated temperature does produce significant morphological changes as
shown in FIG. 4D. The crystals no longer have sharp edges and appear to
be highly curled and broken. This is likely due to the dissolution of
framework silica.

[0135]FIGS. 5A, 5B, 5C and 5D show low magnification TEM images of various
samples. MCM-22(P) has a thin flake-like morphology as shown in FIG. 5A,
with layers stacked over each other in a lamellar arrangement as shown in
FIG. 5B. Swelling at room temperature does not lead to any major changes
in the particle morphology, as already seen by SEM and further shown by a
TEM micrograph in FIG. 5C. In contrast, FIG. 5D, which shows the
morphology of the material swollen at 80° C., clearly shows the
loss of lamellar morphology and crystal facets. Layers appear to be
curled, partially delaminated and out of registry.

[0136]High-resolution TEM (HRTEM) was used to examine the structure of
individual layers and the associated gallery spacing. FIGS. 6A, 6B, 6C,
6D, 6E and 6F show TEM micrographs for various specimens. Structural
schematics of MCM-22(P) have been overlaid on the TEM micrographs in
order to guide visualization, MCM-22(P) in FIG. 6A shows approximately
2.5 nm thick layers. Each layer appears as two dark bands separated by a
bright band. The bright band is attributed to the 10-MR pore system
within the layer, while the dark bands appear due to the higher silica
density in the remaining parts of the layer (top and bottom). The gallery
space between the two layers also appears as a bright band. MIN-1 in FIG.
6B displays well-ordered layers with an expanded interlayer distance
relative to MCM-22(P). FIG. 6C is a TEM image of the material obtained by
acidification of MIN-1. This image shows the layer spacing and structure
corresponding to MCM-22(P) and is consistent with FIG. 6A. This provides
another piece of evidence, in addition to XRD, for the reversible
swelling of MCM-22(P) at room temperature. TEM images of MCM-22(PS-80)
are shown in FIGS. 6D, 6E and 6F. MCM-22(PS-80) shows a different
morphology than MIN-1. Here, crystals appear to be much more fragmented,
with curled layers and amorphous regions. As evidenced by FIGS. 6D and
6E, the layers generally lack the long range ordered stacking obtained
for MIN-1. FIG. 6E shows a swollen particle with a part containing well
resolved layers and another part that looks amorphous. Although some
ordered layers with increased inter layer spacing were observed, as shown
in FIG. 6F, such regions make up a minor fraction of the specimen
examined. It is concluded that the hot basic conditions used for swelling
the sample partly degrade the structure and dissolve the framework silica
in some regions,

Pillaring of Swollen Materials

[0137]MIN-1 was pillared to make an analog of MCM-36 designated as MIN-3.
FIG. 7A illustrates a XRD pattern obtained after pillaring MIN-1 (with a
second curve showing a five (5) times magnification). This pattern is
characteristic of a MCM-36 material with an intense low angle 001 peak at
the 2θ value of 2°. In contrast to MCM-36, the 002 and 003
reflections are, surprisingly, plainly visible. The presence of these
reflections indicates that the material retains long range order even
after pillaring and differentiates MIN-3 from MCM-36.

[0138]FIG. 7B illustrates a pillared material obtained from MCM-22(PS-80)
(with a second curve showing a five (5) times magnification). The XRD
pattern is grossly similar to MIN-3, except that the peaks are broader
and the 002 and 003 reflections are not visible, indicating the absence
of long range order.

[0140]Nitrogen adsorption experiments further confirm successful
pillaring. FIG. 9 shows the nitrogen adsorption/desorption curves for
MCM-22 and MIN-3. For MIN-3, the increase in adsorption up to a relative
pressure (P/P0) of 0.4 clearly indicates the presence of
mesoporosity created by pillaring, MCM-22, on the other hand, saturates
at a relative pressure of 0.1. The BET surface area (See Brunauer S. et,
al., Journal of The American Chemical Society, 60, 309 (1938)) of the
pillared material was found to be 934 m2/g, which is significantly
higher than the value of 560 m2/g obtained for MCM-22.

Polystyrene-MIN-2 Nanocomposites

[0141]Polymer-MIN-2 nanocomposites with polystyrene as the choice of
polymer were prepared by solvent casting and melt blending techniques.
For solvent casting, toluene was found to be a suitable solvent to
disperse the swollen material based on the optical clarity of the
dispersion. FIG. 10 shows a TEM micrograph of the polystyrene MIN-2
nanocomposite prepared with toluene as the solvent. Exfoliated single
layers (indicated by white arrows) are visible along with partially
exfoliated and intercalated layered structures (black arrows). The area
marked by the white box on the image shows a crystal in the process of
exfoliation (as seen by the curving and detachment of layers). Carbon
present on the TEM grid used to hold the sample is indicated with a black
arrow, to distinguish it from the sample.

[0142]FIG. 11A shows a TEM micrograph of the polystyrene-MIN-2
nanocomposite prepared by solution or solvent casting as described above.
FIG. 11B shows a TEM micrograph of the polystyrene-MIN-2 nanocomposite
prepared by melt compounding. A number of individual exfoliated layers
(some indicated by white arrows) along with a polymer-intercalated
stack-of-layers (indicated by a black arrow) are visible in both
micrographs.

Example 2

Polystyrene-MIN-2 Nanocomposites

[0143]Other nanocomposites were prepared by the melt blending procedure
described in Example it except that the mixture was blended sequentially
at 120° C. for 10 min, 170° C. for 10 mM, 15° C. for
5 min and 190° C. for five (5) min and finally extruded out at
140° C. A screw speed of 300 rpm was used for blending, instead of
the 350 rpm as in Example 1, FIG. 11C shows a TEM micrograph of the
nanocomposite prepared under these conditions. FIG. 11C further shows
that the extent of exfoliation has improved as compared to FIG. 11A, as
seen by a greater number of individual exfoliated layers (some indicated
by white arrows) and a very few polymer-intercalated stack of layers
(indicated by a black arrow).

[0144]The polystyrene nanocomposites prepared using the melt compounding
technique described in Example 1 were subjected to depolymerization.
Specifically, ten (10) g of nanocomposite was placed in a quartz tube and
evacuated by connecting to a vacuum pump. At the same time, the tube was
heated to 350° C. (40° C. above the ceiling temperature of
polystyrene). The heating and evacuation process was continued for six
(6) days, during which most of the polystyrene was converted into styrene
and escaped from the tube as vapors. Subsequently, the evacuation was
stopped and air was blown continuously through the quartz tube. The
temperature was then raised to 540° C. to calcine the exfoliated
zeolite layers (MIN-2) left behind in the tube. Calcination was continued
for approximately five (5) hours, after which tube was cooled to room
temperature and MIN-2 powder was removed. The MIN-2 powder was analyzed
using XRD and TEM. The XRD pattern produced is shown above in Table 2A.

[0145]FIG. 12 shows XRD patterns for MIN-2 powder. The XRD peaks of MIN-2
were found to be much broader as compared to MIN-1. This is due to the
fact that MIN-2 comprises predominantly exfoliated layers, which do not
have correlation with each other.

[0146]FIG. 13 shows a TEM micrograph of a MIN-2 powder. The TEM image of
MIN-2 shows highly crystalline exfoliated layers. The pore structure of
layers is visible in the edge view of layers. In contrast to conventional
materials, the novel materials disclosed herein and shown in the figures,
reveal that pore structure and the overall morphology of the layers is
preserved.

[0148]0.05 g of MIN-2 powder was dispersed in ten (10) g of
tetrahydrofuran (THF) by ultrasonication, followed by successive addition
of the 0.01 g of 7.5 wt % potysulfone solution in THY. After 2 h of
vigorous stirring at 70° C., 3.5 g of 30 wt % polysulfone solution
was added. The mixture was allowed to be mixed for 2 h at 70° C.
and then sonicated for 1 h. The mixture solution was poured on a glass
plate and cast using doctor's blade and solvent was allowed to evaporate
overnight. The membranes were peeled off from the glass surface, annealed
under vacuum at 120° C. for 24 hours and tested for separation
using the setup described elsewhere (see Choi S. et. al, Journal of
Membrane Science, 2008, (1-2), 145-152). For comparison purposes, a pure
polymer membrane was also cast using the procedure described above, but
without using MIN-2 powder.

[0149]The polysulfone-MIN-2 membrane showed a 50% selectivity enhancement
for the hydrogen/carbon dioxide pair. The selectivity was found to be
about three (3) for the mixed matrix membrane, as compared to two (2) for
the pure polymer membrane.

Example 5

MCM-22/Silica

[0150]The pores of MCM-22 are transport limiting pores which are
appropriately sized to separate hydrogen (H2) from carbon dioxide
(CO2) and nitrogen (N2). Specifically, H2 can pass through
the pores in these crystals, while N2 and CO2 follow a more
tortuous path around the crystals.

[0151]In this testing, as shown in FIG. 14A, MCM-22/silica supported films
140 comprising a MCM-22/silica film 142 and support 144 were produced. In
this embodiment, the support 144 is an alumina support. The MCM-22/silica
supported films 140 were produced using a layer-by-layer deposition
technique to build five alternating layers (A-E) of MCM-22 condensed
crystal layer sets 146, shown schematically in FIG. 14A, within a
mesoporous silica matrix 148 onto the support 144. Each MCM-22 condensed
crystal layer set 146 is disc-shaped and comprised of about 40 layers 145
condensed together. The MCM-22 crystal layer sets 146 were essentially
used as tiles for the formation of these films 142. Each MCM-22 crystal
layer set 146 is approximately 1000 nm in diameter, has a thickness 149
of about 100 nm, and has approximately 40 transport limiting pores
arranged in series (not shown). The total thickness 150 of the film 142
is about 1000 nm. The flow of hydrogen and nitrogen through the film 142
is also shown schematically in FIG. 14A. FIG. 14B further provides a top
view of the supported MCM-22/silica film 142 shown in FIG. 14A.

[0152]The MCM-22/silica supported films 140 produced herein exhibited
H2/CO2 and H2/N2 fluxes in the range of 0.005-0.01
mol/m2-s, with one bar trans-membrane pressure difference, as shown
in FIG. 15A. In these films, H2 has to cross approximately 40
transport limiting pores per layer of MCM-22 and approximately 200 pores
to pass through the entire five-layer thick film. The H2/CO2
and H2/N2 ideal selectivities were approximately 10 and 50
respectively, at 220° C., as shown in FIG. 15B. Such results
confirm that MCM-22 is capable of greatly enhancing gas separation
capability.

[0153]Referring again to FIG. 14A, CO2 and N2 not capable of
passing through the transport limiting pores of the crystal layer sets
146, pass through larger, more tortuous paths 152 and 154 between the
crystal layer sets 146 (path 152) and/or through larger pores of the
crystal layer sets 146 (path 154) as shown in FIG. 14A. For hydrogen, the
effective thickness of the membrane is the actual 0.5 micron thickness.
However, for CO2 and N2 the effective thickness of the film 142
is much larger, because of the tortuous path they have to take. A
reasonable estimate of the length of path for these gases is (width of
MCM-22 crystal) plus (film thickness), or approximately 5,500 nm.

[0154]FIG. 16 is a schematic of transport paths for hydrogen and carbon
dioxide through a MCM-22 film made using MCM-22 disk-shaped crystals in
an embodiment of the present invention.

Example 6

LBL Assembly to Make Thin Film Coatings of MIN-2 on Porous Alumina
Substrate

[0155]Porous substrates of alumina were used for making thin films of
MIN-2. The fabrication of substrate has been described elsewhere (Lai,
Z.; Tsapatsis, Nicolich, J. P., Adv. Fund. Mater. 2004, 14 (7), 716-729).
Prior to deposition of films, the alumina support was coated with
mesoporous silica to reduce the roughness of substrate using a procedure
described elsewhere (J. Choi, Z. Lai, S. Ghosh, D. E. Beving, Y. Yan and
M. Tsapatsis, Ind. Eng. Chem. Res. 2007 46 (22) 7096-7106). An aqueous
polyelectrolyte solution and aqueous MIN-2 dispersion were prepared for
thin film deposition. A one (1) wt % aqueous solution of positively
charged polyelectrolyte was prepared by diluting a 20 wt % aqueous
solution of poly(diallyldimethylammonium chloride) (PDDA) (Sigma-Aldrich,
St. Louis, Mo.) with distilled water. An aqueous dispersion of MIN-2 was
prepared by dispersing 0.1 g of MIN-2 powder in 100 g of water,
subjecting the dispersion to ultrasonication (Branson 5510, Emerson
Electric Co., St. Louis, Mo.) for about 1.5 hrs, leaving the dispersion
undisturbed for about 12 hours to allow big agglomerates to settle down,
and gently decanting the top fluid leaving behind the settled
agglomerates. This decanted fluid was used for making coatings by LBL
assembly method.

[0156]Thin film coatings were prepared by first dipping a support in a one
(1) wt % aqueous polyelectrolyte solution described above, for about five
(5) min. The support was then rinsed twice with fresh water for about one
(1) minute each (rinsing step), dried for about one (1) minute under air
flow (drying step) and then dipped in the aqueous MIN-2 dispersion
described above for about five (5) minutes followed by an additional
rinsing and drying step. This process was repeated to deposit three
alternate layers each of polyelectrolyte and MIN-2, Following the
deposition cycles, the substrate-film assembly was heated to 540°
C. for approximately five (5) hrs to burn off the polyelectrolyte.

[0157]FIGS. 17A and 17B show the SEM images of MIN-2 thin film coating on
alumina support prepared by LBL method. The film appears continuous and
the support surface is covered with MIN-2. These films can be very useful
as hydrogen separation membranes and for corrosion protection
applications.

Example 7

(Prophetic)

MIN-2 Films

[0158]MIN-2 films will be produced, characterized and tested. FIG. 18
provides a simple schematic of a membrane made using a MIN-2 type
material having exfoliated layers, while FIG. 19 shows a simple schematic
of a mesoporous silica/MIN-2 composite membrane in an embodiment of the
present invention.

[0159]The MIN-2 crystals to be used in this testing to make various films
comprise thinner tiles having a thickness of about 2.5 nm and a diameter
of about 250 nm. Instead of 40 transport limiting pores, each MIN-2
crystal has only one such pore. One transport limiting pore thick
crystals are expected to be sufficient for separation of hydrogen, when
stacked on top of each other.

[0160]A deposit of the same 0.5 micron thickness film will be made as
discussed above in the MCM-22/silica films in Example 5. However, the
resulting film will contain approximately 200 MIN-2 tiles, as compared
with the approximately five (5) with the MCM-22 crystals. It is expect
that H2 will experience no significant additional resistance, since
its dominant transport pathway of diffusion through the pores remains
similar. However, CO2 and N2 will experience an increasingly
tortuous path for transport as the number of layers and, correspondingly,
their overlapping increases.

[0161]For the membrane containing 200 layers of MIN-2 (2.5 nm)×(250
nm), it is estimated that the tortuous path is approximately 50,500 nm,
which represents at least a ten-fold increase from the MCM-22/silica
films discussed in Example 5. The expected selectivity of these membranes
at 220° C. is therefore expected to be at least ten times better
than MCM-22/silica films giving H2/CO2, H2/N2
selectivity and H2 permeance of 100, 500, and 0.005-0.01
mol/m2-s-bar, respectively.

[0162]Additional testing is expected to result in films which are less
than 0.5 microns in thickness, but not eight times thinner than the
MCM-22/silica films of Example 5. As a result, such films are expected to
have a selectivity enhancement of at least one (1) to ten (10) times the
selectivity demonstrated by the MCM-22/silica films of Example 5. Such
films are also expected to have a permeability enhancement of at least
one to eight (8) times the permeability of the MCM-22/silica films of
Example 5. However, the exact level of selectivity and permeability
enhancement will depend on the actual thickness of the film. In one
embodiment, such films may demonstrate at least an eight-fold increase in
flux, thus reaching an expected value of 0.04 to 0.08 mol/m2-s-bar.

[0164]In one embodiment, the invention provides a novel oxide material
(MIN-1) comprising YO2; and X2O3, wherein Y is a
tetravalent element and X is a trivalent element. In one embodiment,
X/Y=0. In one embodiment, Y/X=30 to 100 is provided. MIN-1 is a swollen
material derived from MCM-22(P) having a different x-ray diffraction
pattern as compared to swollen MCM-22(P) prepared by conventional
methods. MIN-1 has a highly ordered structure with increased layer
spacing, and exhibits little or no degradation of in-plane layer
morphology. In one embodiment, MIN-1 is produced by swelling under high
pH conditions (i.e., at 13.6 r above) followed by repeated washings with
water. 1.11 one embodiment, MIN-1 is produced at room temperature
conditions.

[0165]An unexpected and surprising feature of the swollen material is that
it can be reversibly deswollen back to MCM-22(P) by acidification, thus
indicating a high degree of layer structure preservation upon swelling.
This is in contrast to the material produced by conventional high
temperature swelling processes, which cannot be reversed back to
MCM-22(P) structure. The swelling procedure described herein is well
suited for polymer nanocomposite and thin coating fabrication, which
requires swelling of MCM-22(P) layers with retention of crystal structure
to maintain the high aspect ratio of the layers.

[0166]MIN-1 may further be pillared to produce a pillared material
designated as MIN-3, which retains layers with composition and structure
closer to the one present in MCM-22(P). MIN-3 is expected to have
distinct catalytic and stability properties as compared to conventional
pillared materials.

[0167]MIN-1 can further be combined with a polymer (i.e., polymer matrix)
to produce a nanocomposite having predominantly exfoliated layers with a
few intercalated crystals and designated herein as composite MIN-2. The
polymer may be removed from composite MIN-2, such as be depolymerization,
produce MIN-2. MIN-2 is expected to be useful in a wide range of
applications, such as catalysts, thin films and coatings.

[0168]All of the publications, patents and patent documents are
incorporated by reference herein, each in their entirety, as though
individually incorporated by reference. In the case of any
inconsistencies, the present disclosure, including any definitions
therein, will prevail. The numbered references correspond to footnotes
throughout the application.

[0169]Although specific embodiments have been illustrated and described
herein, it will be appreciated by those of ordinary skill in the art that
any procedure that is calculated to achieve the same purpose may be
substituted for the specific embodiments shown. For example, the method
used for exfoliation discussed herein may be useful for a variety of
layered materials such as clays and aluminum phosphates. This application
is intended to cover any adaptations or variations of the present subject
matter. Therefore, it is manifestly intended that embodiments of this
invention be limited only by the claims and the equivalents thereof.